Polymeric arsenic compounds



United States Patent PoLvMEmc ARSENIC coMPoufins John R. Van Wazer,Ladue, and Kurt Moedritzer, Webster Groves, Mo., assiguors to MonsantoCompany, St.

Louis, Mo., a corporation of Delawar No Drawing. Filed Dec. 31, 1964,Ser. No. 422,549,

19 Claims. c1. 23-293 p ABSTRACT OF THE DISCLOSURE carbyl radical havingfrom" l'to 20 carbon atoms. The

compositions of the present invention have utility as biologicalcomp'ounds such as insecticides, fungicides, and herbicides, as well asin the eradication of vermin.

The present invention" relates to novel substituted arsenic-compoundscontaining-oxygen or sulfur. It is an object of the invention to preparecertain novel compounds containing arsenic and oxygen or sulfur andexisting as polymeric compounds.

The compounds contemplated in the present invention have the generalover-all composition where x and y are positive numbers, mis an integerfrom 2 to 1000, and x+y=3. In the above formula Y is selected from thegroup'consisting of oxygen and sulfur, X is a radical selected from thegroup consisting. of the halogens such as fluorine, chlorine, bromineand iodine;

alkoxy radicals,'-OR; dialkyl amine radicals, NR

and mercapto radicals, SR, where R is 'ahydrocarbyl radicals having from1 to 20 carbon atoms such as alkyl, cycloalkyl and aromatic (620' carbonatom) radicals.

The general method for the preparation of the present compounds is bythe agitationtogether of I Q AS203 or As S and a modifying arsenicsource AsX where X has the meaning set forth above.

The ratio between the starting components e.g the arsenic oxide orsulfide compound and the modifying arsenic compound is broadly inthcmolar proportion of from 100:-1 to 1:100, withcertain ratios givinghigher polymeric products. Polymeric forms of the present compositions,e.g., having from 2 to 1000 arsenic atoms per molecule are obtained whenusing a range of mole proportions of 0.001 to 10.0 moles of the arsenicmodifying compound AsX relative to a mole of the arsenic sulfide oroxide. The lower portion of this range favors the production of thehighest molecular weight products.

The general classes of specific products obtained in the practice of thepresent invention, and falling within the above general formula (witht-liecentral -O or S- radical being represented by Y) existing as alinear, and

branched chain structure are as follows:

dimer 3,394,992 Patented July 30, 1968 rings rings with branches Thegeneral procedure for the preparation of the presfent compounds is toagitate a mixture of the respective components, for example, thecompound A5 0 or AS283 together with an arsenic source AsX as describedabove,

for example, arsenic trifluoride, in the desired proportion, such as 1:5(molar) and with'the mixture maintained at a temperature in the range offrom 0 C. to 150 C. A

solvent is not necessary, although it is possible to operate in thepresence of a hydrocarbon solvent e.g., benzene,

toluene, pentaneor decane solvent or a halocarbon solvent such as carbontetrachloride, hexafluoroethane, etc. The

pressure is not a controlling variable so that the reaction may beconducted under vacuum or pressure conditions. However, it is desirableto conduct the reaction in a sealed tube or under an inert gasatmosphere for example nitro gen or argon. The general method is asfollows: Depending on the equilibrium composition desired, from 8.3 g.to

0.2 g. of arsenic trifluoride and from 0.2 g. to 2.0 arsenic .sulfide ortrioxide (mole ratio of 0.2 to 20 relative to the A 8 or As O areaccurately weighed into 5 mm. ID. thick-walled 'Pyrex tubes which arepreviously kept in an over to remove sorbed water and are then flushedwith pure, drynitrogen. The tubes are sealed and thenheated for 8 hr. atC. The contents of each tube are completely homogeneous under theseconditions. \After heating, the tubes are rapidly cooled to 0 C. and arethen opened. This operation should be conducted in a hood, being carefulto avoid contact of the products with the operators skin, such as by theuse of rubber gloves or 'a dry box. The low temperature may result inthe appearance of a solid phase of the product which can be removed. Ifdesired the sample tubes are carefully warmed until the contents areagain homogeneous. A portion of the contents are transferred directlyinto a precision-bore, thin-walled tube and investigated by fluorinenuclear magnet-ic resonance. The remaining material is used in a diluteform favoring N. M.R. resolution by dissolving the sample in three partsof toluene and the resulting solution transferred into another N.M.R.tube and also investigated by fluorine nuclear magnetic resonance. Thesystem is found to attain equilibrium rapidly, e.g., upon dissolution ofthe A5203 or AS353. The separation of the individual species otrnolecples in the product can be,elfected by low temperaturechromatography or by low temperature crystallization e.g. from pentaneat 78 C.

The following examples illustrate specific embodiments of the presentinvention.

Example 1 A quantity of 2.64 g. of arsenic trifluoride is combined with3.96 of arsenic trioxide (1:1 mole ratio) in a reaction tube and heatedfor several hours at 120 C. The resulting polymeric reaction product isa viscous oil of the overall composition AsOF, containing an equilibriummixture of various O- bridged arsenic fluorides as polymer chains havingbranching points. The average number of As atoms per molecule rangesfrom to 15.

Example 2 Example 3 An amount of 12.65 g. of arsenic trichloride isreacted with 3.96 g. of arsenic trioxide (3.5c'1 mole ratio) in areaction flask maintained at 130 C. under refluxing conditions with thecondenser vented to the atmosphere and protected from moisture. Theresulting product has an overall composition of ASO y 55Cl1 9 andconsists mainly of the species Cl AsoAsCl Example 4 A quantity of 12.6g. of arsenic tribromide is mixed with 3.96 g. of arsenic trioxide (2:1mole ratio) and heated at 120 C. for hours. The resulting viscousreaction product has the overall composition AsO Br and is a linearpolymer with branching groups with the aver age number of As atoms permolecule ranging from 10 to 25.

Example 5 A 22.8 g. sample of arsenic triiodide is heated together at150 C. with 3.96 g. of As O (3:1 mole ratio) in a hydrocarbon solvent.After removal of the solvent the residue shows the overall compositionASO0 67I1 57 and is a chain polymer with branching points with theaverage number of As atoms per molecule ranging from 8 to 20.

Example 6 A quantity of 2.52 g. of trimethylarsenite is combined with3.95 g. of As O (0.75:1 mole ratio) in a reaction tube and heated forseveral hours at 130 C. The result- 0 ing reaction mixture is a viscousliquid with the overall composition ASO1 09 (OCH The product is acrosslinked polymer having to 100 As atoms per molecule.

Example 7 An amount of 12.42 g. of trisdimethylaminoarsine is mixed with3.95 g. of A8303 (3:1 mole ratio) and heated at 100 C. over a period of10 hours. The resulting reaction product analyzes as AsO [N(OH andconsists mainly of the linear species having from 2 to 8 As atoms permolecule.

Example 8 A quantity of 12.42 g. of trisdimethylaminoarsine is mixedwith 4.92 g. of AS253 (3:1 mole ratio) and heated at 100 C. over aperiod of 24 hours. The resulting viscous reaction product analyzes asAsS [N(CH and is a polymer with the average number of As atoms permolecule ranging from 2 to 10.

Example An amount of 8.32 g. of trisdimethylaminoarsine is heated with4.92 g. of As S (2:1 mole ratio) at '150 C. over a period of 2 4 hours.The resulting viscous product has an overall composition AsS [N(CH withan average number of As atoms per molecule ranging from 10 to 50.

The compounds of the present invent-ion have utility using suitableprecautions as biological compounds such as insecticides, fungicides andherbicides, as well as in the eradication of vermin, such as rats. Thecompounds should be handled with the use of conventional protectiveequipment such as rubber gloves, masks, and suitable protectiveclothing.

What is claimed is:

1. Polymeric arsenic compounds having the formula where x and y arepositive numbers, m is an integer from 2 to 1000, and x+y=3, Y isselected from the group consisting of oxygen and sulfur, and X isselected from the group consisting of fluorine, chlorine, bromine andiodine; alkoxy radicals, OR; dialkyl amine radicals, NR;,; and mercaptoradicals, SR; where R is a hydrocarbyl radical having from 1 to 20carbon atoms.

2. As a composition of matter, polymeric(AsOF) where m is an integerfrom 2 to 1000.

3. As a composition of matter, pO1yl1'l6llC(AS0 F where m is an integerfrom 2 to 1000.

4. As a composition of matter, polymeric where m is an integer from 2 to1000.

5. As a composition of matter, polymeric where m is an integer from 2 to1000.

6. As a composition of matter, polymeric where m is an integer from 2 to1000.

where m is an integer from 2 to 1000.

7. As a composition of matter, polymeric where m is an integer from 2 to1000.

8. As a composition of matter, polymer where m is an integer from 2 to1000.

9. As a composition of matter, polymeric where m is an integer from 2 to1000.

10. As a composition of matter, polymeric where m is an integer from 2to 1000.

11. Process for the preparation of polymers having the formula x/2 y)mwhere x and y are positive numbers, m is an integer from 2 to 1000 andx+y=3, Y is selected from the group consisting of oxygen and sulfur, andX is selected from the group consisting of fluorine, chlorine, bromineand iodine; alkoxy radicals, -OR; dialkyl amine radicals, NR andmercapto radicals, SR; where R is an alkyl radical having from 1 to 20carbon atoms, which comprises agitating together an arsenic compoundhaving the formula ASX with As Y in the mole range of 0.001:1 to 10:1,at a temperature of from 0 C. to C., and thereafter separating thepolymeric (AsY X 12. Process for the preparation of polymeric [AsOF]where m is an integer from 2 to 1000 which, comprises agitatingtogether, AsF with AS203 in the mole proportion of about 1:1 at atemperature of from 0 C. to 150 C., and thereafter separating the saidpolymer.

13. Process for the preparation of polymeric where m is an integer from2 to 1000, which comprises agitating together AsF together with AS203 inthe mole ratio of about 0.5 :1 at a temperature of from 0 to 150 C., andthereafter separating the said polymer.

14. Process for the preparation of polymeric where m is an integer from2 to 1000, which comprises agitating AsCl together with AS203 in themole ratio of about 3.5 :1 at a temperature of from 0 C. to 150 C., andthereafter separating the said polymer.

15. Process for the preparation of polymeric Where m is an integer from2 to 1000, which comprises agitating together AsBr with AS203 in themole proportion of about 2:1 at a temperature of from 0 C. to 150 C.,and thereafter separating the said polymer.

16. Process for the preparation of polymeric where m is an integer from2 to 1000, which comprises agitating together AsI with AS203 in the moleproportion of about 3:1 at a temperature of from 0 C. to 150 C., andthereafter separating the said polymer.

17. Process for the preparation of polymeric where m is an integer from2 to 1000, which comprises agitating together As(OCH and AS203 in themole proportion of about 0.75:1 at a temperature of from 0 to C., andthereafter separating the said polymer.

18. Process for the preparation of polymeric where m is an integer from2 to 1000, which comprises agitating together As[N(CH and AS203 in themole proportion of about 3:1 at a temperature of from 0 to 150 C., andthereafter separating the said polymer.

19. Process for the preparation of polymeric where m is an integer from2 to 1000, which comprises agitating together As[N(CH with AS283 in themole proportion of about 3:1 at a temperature of from 0 C. to 150 C.,and thereafter separating the said polymer.

References Cited lander et al.: Zeitschrift fur Anorganische undAllgemeine Chemie, vol. 302, November 1959, pp. 158-161.

EDWARD J. MEROS, Primary Examiner.

H. S. MILLER, Assistant Examiner.

UNITED STATES PATENT OFFICE (Ea/b:

EERTIFICATE OF CORRECTION Patent No. 3 39u 992 Dated Jul 30. 1568 I tor)John R. Van *fazer 4-31: al

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 1, line &3 "radicals" should m3: radical Column 2 lines l-S theformula II I}: v u

A3 "5 m As should read y' \l h L i H [as '.c'- As r As Colmrm '2 line51, "T .D. should be i. .d.

Column 2 line 53 "oven" should "he over Column 2 lines 68 8 7G EME..efnoulr be n. rnnr.

Column line 38 the 'Jorcis here m an in'tew from 7? co 1 G flPfB'i:pnearin before formula should omi. titer? (,mlumn H lino +7 the word"fiOl'JIfli-ZI" Shoul he 701V- ilolurim 5 line 1]. the Formula "I: Am"C]. I zzuoull l J?) 1.1m

C l un'm d 1 L22 1 "0" "@0113 1 be 3C SIGNED AND SEALED @EAL Atteat:

Edward M. Fletcher, It: mm Attesting Officer comiuim Pam

